Hydrogen fluoride alkylation of paraffins



Patented May 14, 1946 r i f 2,400,386,

HYDROGEN FLUORIDE ALKYLATION OF PARAFFIN S John C. Bolinger, San Marino, Andrew K. Brumbaugh, Inglewood, and James H. Curtis, Be-' dondo Beach, Calif., assignors to Socony- Vacuum Oil Company, Incorporated, New York, N. Y., a. corporation of New 'York Application November- 15, 1944, Serial No. 563,538

1 Claim. (or. 260-4834) This invention has to do with processes for the alkylation of paraffln hydrocarbons witholeflns, such as the'alkylation of isobutane with butene'to form isooctane, and particularly with such processes wherein the catalyst used is hydrofluoric acid or material of the type of that catalyst, such as certain fluorides, other halides and the like;

In such processes the general scheme of oper-- -ation is one in which a hydrocarbon feed stream 10 used acid the polymers, which are a 'minor side containing theparafflnic and oleflnic reactants is contacted with the liquidcatalyst and the reaction mixture passes toa settler in which a hydrocarbon phase separates from an acid phase. The acid is returned to the contacting step, a

small proportion-of the cycled stream being splitoil and treated to remove impurities. The hydrocarbon phase is heated to remove entrained acid, which is returned to the contacting step. The deacidifled hydrocarbons are twice fractionated, to remove isobutane, which is recycled, and to remove normal butane, which'is withdrawn from major elements is conventional, is illustrated in 3 the attached diagrammatic drawing, to which reference is here made. v

A liquid to liquid contactor l is supplied with an isobutane -i-butene mixture at 2 and with a recycled stream oi isobutane at l. The contactor is also supplied at 4 with; a small quantity. of

, make-up acid (hydrogen fluoride) as required,

and-at I with a larger stream 01' recycled acid.

After contacting under suitable conditions of a r and temperature the reaction e returned to the base of the tower for heating purposes, are directed through conduit 32 to a' passes-through conduit 6 to a settler-l inwhicli an acid phase (below) separates from a hydrocarbon phase (above). The acid phase is with-. drawn from. the settler and divided into two streams, the major portion returning directly to the contactor through conduit 8. A minor proportion 01 the order 021% to 2% by volum ,is diverted through a conduit Ito an acid recenerator 8. This element is a plate or packed tower,

Y heated by circulation of bottoms through a loop system as at 30.

III including a reboiler H and having a valvecontrolled outlet is thro sh which a "small quantity of relatively nonvolatile hydrocarbon (the socalled "polymer") is more or less continuously withdrawn from the system.

In the acid regenerate: the volatile constituents of the diverted acid stream (acid, water and dissolved or entrained volatile hydrocarbons) are vaporized, passing through It to-condenser I and thence through conduit l5 and isobutane re- 5 cycle main 3 to contactor-L This tower is usually refluxed with isobutane which may be withdrawn from recycle main 3 upstream from its junction with conduit l5, asthrough conduit I6.

By this step of distillation of a side stream of product of the catalysiaare prevented from building up in the acidcycle.

' The hydrocarbon phase, which contains some entrained acid, is withdrawn, from "the settler through conduit I1 and introduced into the upper part of an acid stripper l8, whichmay be any prererred form of fractio'n'ating tower. This element is heated'by the circulation or bottoms through a loop I! including a reboiler Ill. The stripper distils out the entrained acid, together with some volatile hydrocarbons, the vaporpassing through conduit 2| to a condenser, the condensate from which is disposed oi in a manner to be described.

The major proportion of the bottoms. a substantially acid-free mixture of various hydrocarbons, is directed through conduit 24 to a flrst iractionating tower 2!. (the deisobutanizer).

This element is a plate fractionating tower heat-v ed by a circulation of bottoms through a loop 26 including a reboiler 21. The overhead from the tower, consisting or excess isobutane, passes through conduit 28 to a condenser-28 from which R a portion of the condensate is returned as at 30 as reflux liquid. The remainder oi the condensate is. in ordinary practice, returned through conduit 3| to isobutane recycle main '3 and through it to the contactor.

The bottoms from tower 25, aside from the part second iractionating tower is (the debutanizer) which is heated by a circulation of bottoms through a loop 34 including a reboiler ii. The

overhead fraction from this tower consists of normal butane, which passes as vapor through it to a. condenser 81. The condensate is in part returned-to the top of the tower. as at ll, as reflux liquid, the remainder being withdrawn from the u by contact. with a solid adsorbent and or treetionating into light and heavy alkylates, with which we are not here concerned.

We return now to the disposal of the overhead stream from the acid stripper [8, which is the subject matter of the present invention.

The conventional procedure is to return the overhead from the acid. stripper directly to settier 1, in which it joins the reaction mixture coming from the contactor. The feed to the contactor must contain a large excess isobutane over the calculated quantity, to ensure complete utilization of the butene content of the ieedstream. The overhead from the acid stripper consists to a large extent of this excess isobutane and to a smaller extent of acid entrained in the reaction mixture; As the hydrocarbon phase in settler l is free from butenes, none of the isobutane returned to it in the present practice is consumed. The result is the establishment of a wholly nonfunctional cycle, including the settler and the stripper, in which isobutane is repeatedly distilled without undergoing any change.

We improve on this present practice in delivering the stream of condensate from condenser 22 (the overhead from the acid stripper consisting, as said, largely of isobutane) into a, secondary settling vessel 4| in which a layer oi acid 42 separates from a hydrocarbon layer Q3. The acid is continuously withdrawn from the lower layer and passes through conduit 44 to primary settler 1, from which it is cycled back to the con-. tactor as first described. The isobutane is withdrawn irom th'e upper layer and passes through conduit 45 into the deisobutanizer 25 from which is at least equal to the quantity brought to the settler as a component of the reaction mixture, the load on the stripper is reduced by approximately one-half in directing the hydrocarbon content of the stripper overhead to the deisobutanizer, from which it returns to the initial contacting step in which it is useful.-

The load on the deisobutanizer is little if at all increased by this change; as the isobutane from the secondary settler is substantially free from heavier hydrocarbons and may thus be utilized to replace part or all of the reflux liquid otherwise returned to this tower from its own overhead stream,

We claim as our invention:

In an alkylation process involving the steps of contacting a feed stream consisting substantially or butenes and isobutane with a body or liquid hydrofluoric acid, of withdrawing from said body a hydrocarbon stream consistingsubstantially of alkylate and unreacted isobutane and including a, modicum of said acid; of settling from said stream a portion of said included acid and returning saidacid to said body, of subjecting said stream to a first distillation in which the remainder of said acid together with a portion of said isobutane is removed from said hydrocarbon stream, of subjecting the residual stream to a second distillation in which the remainder of said isobutane is separated from said alkylate and of returning said last isobutane to the feed. stream entering said acid body: the steps of condensing the vapors resultingfrom said first distillation, of parting said condensate to obtain an-acid phase and a hydrocarbon phase, of returning said acid phase to said acid body, and of introducing said hydrocarbon phase into said second distillation wherein its isobutane content is distilled out and returned to said feed stream.

JOHN C. BOLINGER.

ANDREW K. BRUMBAUGH. JAMES H. CURTIS. 

